Toilet bar



ug 4, 1970 H. E. GARRETT 3,523,089

` TOILET BAR Filed March '7, 1967 2 Sheetsheet 1 Inventor Horace Edward Garret? ug- 4, 97 H. E. GARRETT 3523,@89

TOILET BAR Filed March '7, 1967 2 Sheets-5heet g Inventor Hom e Edward arreif B V660- l y Qfney?, (J" f United States Patent O 3,523,089 TGILET BAR Horace Edward Garrett, Birkenhead, England, assignor to Lever Brothers Company, New York, NX., a corporation of Maine Filed Mar. 7, 1967, Ser. No. 621,206 Claims priority, application Great Britain, Mar. 18, 1966, 11,958/66; Dec. 30, 1966, 58,380/66 Int. Cl. C11d 7/06 U.S. Cl. 252-161 4 Claims ABSTRACT OF THE DISCLOSURE A synthetic detergent toilet bar which consists essentially of (a) a mixture of an alkene sulfonate and a hydroxy alkane sulphonate, said hydroxyalkane sulphonate being a mixture of alkene-3-hydroxy-l-sulphonate, alkane-4-hydroxy sulphonate, and alkane-Z-hydroxy-l-sulfonate, and having no more than 2% by weight of the alkane-Z-hydroxy-l-sulphonate, and (b) a fatty alcohol sulfate.

The invention relates to an improved toilet bar in which the active consists of synthetic detergents.

Bars made entirely from synthetic detergents are usually deficient in plasticity. It has previously been proposed to add a plasticizing amount of water (water has long been known to have a plasticizing effect in any such system) but although this solution to the problem enables the bar to be manufactured on ordinary soap-processing equipment, when the water content is reduced on storage by natural evaporation the bar may crack or become excessively hard so that an undue amount of rubbing is necessary to get a lather when the tablet is taken into use.

Another solution which has been proposed is to combine the unduly hard detergent with one or other of the unduly soft detergents which could not, by themselves, be used to manufacture an acceptable tablet. These soft detergents, however, are often among those least mild to the skin and confer their irritancy to the combination bar in due proportion to the amount added to the combination bar, which amount must, on this account, be strictly limited. It is also known that some hard detergents are unduly irritant, sodium dodecyl sulphate being particularly well known in this respect.

Accordingly, this invention provides a toilet bar consisting essentially of synthetic deterents, wherein the synthetic detergents consist of an alkali metal or alkaline earth metal salt of an alkene sulphonate as herein defined in conjunction with a different non-soap detergent. By alkali metal is meant lithium, sodium, potassium and ammonium and by alkaline earth metal is meant calcium and magnesium.

Such tablets are mild to the skin and possess the desirable attributes of good lathering in hot or cold, hard or soft water in conjunction with a reasonable rate of wear.

Toilet bars which consist essentially of alkane sulphonates and and alkene sulphonates are the subject of our copending British patent application No. 8,532/ 66. Such bars are not within the scope of the present application.

The alkene sulphonates for use in this invention may be obtained by the well-known series of reactions from Fice the actions of S03 or similar sulphonating agents on alphaoleiins. The alkene sulphonates preferred are those which result from reactions of alpha oleiins having C11 2.1 chain lengths, with a strong sulphonating agent, particularly sulphur trioxide in an inert gas such as air, and wherein the liquid olefin and the SOS/air streams are contacted in a reactor designed to ensure a short time of contact i.e. less than l0 minutes, preferably less than l minute, and provided with a means for removing the heat of rehydrolysis followed by neutralisation, or by alkaline hydrolysis yields salts of sulphonic acids. These sulphonic action. A reaction product is obtained which, on acidic acids are complex mixtures of alkane hydroxy sulphonic acids and alkene acids, with a proportion of sulphonic acids of low equavilent weight which are conveniently termed di-sulphonic acids, without implying that they are wholly true disulphonic acids. They may contain in addition to true disulphonic acids (arising in part from a minor proportion of di-olens in the initial olefin feedstock) some short chain monosulphonic acids arising as a result of scission of the oleiin chain.

The immediate reaction product is believed to be a mixture of alk-2z3-ene-1-sulphonic acid and alkane-- sultone. The latter, however, rapidly isomerises to the gamma and delta sultones which on alkaline hydrolysis yield alkane-3-hydroxy-l-sulphonic acid salts and alkane- 4-hydroxy-l-sulphonic acid salts, respectively. The amount of residual sultone is such that less than about 2% of alkane-Z-hydroxy-l-sulphonic acid salts are present in the mixture. The proportions of alkene sulphonate to total hydroxy alkane sulphonate are approximately as 2:1. The disulphonate factor may be as much as 1 proportion (i.e. about 25% of the total product), but by suitable choice of the quality of the olen feedstock and of the reaction conditions (e.g. low concentration of S03 in the S03/ air stream) may be made susbtantially smaller. Products in which the disulphonate content is reduced to as low a value as practicable are preferred. By the term alkene sulphonates herein is intended the total reaction products as described above.

Thin layer chromatography may be used to separate the neutralised product into three zones corresponding, respectively, to the alkane hydroxy sulphonates, the alkene sulphonates and the disulphonates, the relative amounts of which may then be determined.

Alkene sulphonates as dened above, prepared from about C12-C24 alpha-oleiins (which may be obtained from a cracked-paraiiin distillate, or synthesised from hydrocarbons containing fewer carbon atoms e.g. ethylene by the Ziegler or like catalyst, or by dehydration of primary alcohols derived by hydrogenation of esters of naturally occurring fatty acids such as vegetable or animal oils and fats, or in any other manner known to those skilled in the art), particularly such as contain only small proportions of the alkane-Z-hydroxy-l-sulphonates, are particularly suitable for the preparation of toilet tablets as envisaged in the objects of this invention.

A particularly suitable alkene sulphonate is that having C1440 or C14-C16 chain lengths.

The synthetic detergents with which the alkene sulphonates may be blended are for example, Igepon A, Igepon T, Igepon KT, Igepon 702K, salts of higher fatty acid sulphonates or their amides, alkylolamides or esters,

particularly mono-esters of polyalcohols such as glycol, glycerol and pentaerythritol, salts of sulpho-acetic esters of higher fatty alcohols, glyceryl mono-alkyl ether sulphates and sulphonates, glyceryl mono-acyl ester sulphates and sulphonates and fatty alcohol sulphates.

The degree of mildness exhibited by the compositions of the invention is greater than would be expected from a knowledge of the mildness qualities of the ingredients. Further, the bars have satisfactory plasticity and use properties. The undesirable mechanical properties of non-soap detergents which make them diii'icult to prepare as 'bars using the conventional toilet soap processes of milling, plodding and shaping by stamping are not shown by the compositions of the invention.

It has now been found surprisingly that the combination bars comprising essentially alkene sulphonates and fatty alcohol sulphates are not only readily processed to attractive -bars free from cracking owing to reduced hardness, compared with tablets formed from alkyl sulphate as the sole active, but also exhibit marked synergistic lather volume when compared with tablets made from either component alone. The lather creaminess property is also greatly enhanced in tablets in which the alkene sulphonate component lies within the range 10% to 80% of the active.

Accordingly, this invention is particularly concerned with a toilet bar which consists essentially of synthetic detergents, wherein the synthetic detergents consist of an alkali metal or alkaline earth metal Salt of an alkene sulphonic acid, in conjunction with an alkali metal alkyl sulphate.

The alkyl sulphates may be prepared, as is Well known in the art, by the treatment of primary saturated alcohols with strong sulphonating agents. Means of sulphating unsaturated alcohols with retention of the double bond or bonds have also been long known in the art.

Particularly suitable alkyl sulphates are the C1445 sulphates of synthetic primary alcohols. A commercial source of such synthetic alcohols is later described with reference to FIG. 1. Alternatively, alkyl sulphates may be used which are derived from a narrow distillation out of mainly C1146 or C1648 alcohols from natural sources or entirely n-primary alcohols of synthetic origin. A minor proportion of tallow alcohol sulphate, e.g. up to 25% by weight of composition or of the corresponding C16 20 synthetic alcohol sulphates may also be present. Random alkyl sulphates eig. those commercially designated Teepol (RTM) are not envisaged as the major part of the alkyl sulphate component of the bar according to this invention. These improve the lather performance of the bar, but in higher amounts detract from the hardness. The alkyl Z-sulphate may be used in, say, up to 20% of the alkyl sulphate component.

The synergistic lather volume performance shown by the tablets according to the invention is graphically illustrated in the accompanying FIG. l. These tablets contained as alkene sulphonate, a sodium alkene (C1rC1) sulphonate, derived from cracked wax synthetic olens, and as alkyl sulphate, a C11-C15 synthetic sodium alcohol sulphate derived from Dobanol 45 (RTM)1. (A mainly linear synthetic primary alcohol cut comprising mainly tetradecyl and pentadecyl alcohols of which about 30% are isomers of the n-alcohols and carry a short (e.g. methyl) alkyl group on the second carbon atom.) The lather volume test may be described as follows:

The hands of the operator are covered with thin surgical gloves. Water of the desired hardness and temperature is run to a depth of 3 inches into circular clear plastic bowls of l inches diameter at the base and 14 inches diameter at the top. This approximates to 1 Imperial gallon water. 'I'he gloved hands and the tablet are wetted -by dipping and the tablet is twisted in the 'hands in a standardised manner 15 times. The lather on the 1Known as Neodol 45 in the United States.

4 hands is -worked by rubbing the hands back and forth and to and fro in a standardised manner 20 times each 1way (two alternating periods of ten rubs each) and the lather is transferred to a calibrated vessel. The total volume collected from three such operations is recorded as the lather volume.

Replicates by a trained operator may be made with good precision. Although replication between operators is poor, each operator ranks a series of tablets in the same order and records the same relative differences as do the other operators. The results quoted in this specification were obtained by a single trained operator. The graph of FIG. l was drawn smoothly amongst the points as detailed in the examples. It will be appreciated that the order of experimental error is in the region of $30 mls.

It will be understood by those skilled in the art that essentially similar results are obtained if the C1548 sodium alkene sulphonate is replaced by a C1448 or a C16 21, sodium alkene sulphonate made from alpha-olens derived from Ziegler synthetic olens or a C15 20 or C1548 sulphonate from cracked wax olens, and/or if the C1445 synthetic sodium alcohol sulphate is replaced by a C1446 distillation cut of fatty alcohols derived from synthetic n-alcohols, e.g. those manufactured from alpho-oleiins, especially Ziegler oleiins, by the oxo process, natural fats such as coconut oil, or palm kernel oil. A minor proportion of C15 2.1 sulphonates (either Ziegler or cracked paraihn derived) may also be present.

The synergistic lather volume effect is demonstrated by compositions in which the alkene sulphonate is present in amount to 5% of the total active and the alkyl sulphate in amount 5% to 95 of the total active, preferably in respective amounts of 70:30 to 30:70. The total active may comprise at least 75% by weight of the total composition.

The lather creaminess is very marked with the compositions of the invention. The term lather creaminess is well understood by those skilled in the art but is extrernely ditlicult to define. It expresses an intuitive subjective impression compounded of the qualitative appraisal of the mode (most comon size) of bubble sizes, the whiteness of the lather, and, particularly, its resilience or thickness as appreciated by the tactile senses. The creaminess was judged on a scale represented by the Words: very poor, poor, poor-fair, fair, fair-good, good,

very good, excellent, associated with the numerical scale:

The creaminess value of the lather given by the tablets whose lather volumes are given in FIG. l, are plotted in the accompanying FIG. 2. It is clear that the creaminess values of the bars of the invention rise substantially above those expected from a linear interpolation between the yvalues at the extremes of alkene sulphonate and 100% alkyl sulphate.

In the tablets according to the invention, the amount of alkene sulphonate used may be 20-60% and the total of alkene sulphonate and the other selected non-soap detergent is preferably in the range of 50-90% by weight of the composition.

The tablets according to this invention can be improved in respect of their slip property. It is known that many water-soluble polymeric substances of extremely high molecular Weight, when added in very small amounts (usually less than 0.1%) confer a desirable slip in detergent toilet tablets, but that in larger amounts (eg. more than 0.3%) this slipperiness increased to an intolerable degree of sliminess. Such substances include partially hydrolysed polyacrylamides, super-polyglycols (Polyox (RTM)), and sodium polyacrylates. These substances are highly viscous, and also highly viscoelastic in dilute, e.g. 0.5% w./w., solution. The extreme viscoelasticity confers upon the tablet the intolerable sliminess above-mentioned. If the concentration is reduced so as to gain the slip effect without sliminess, the solutions are no longer able t conides gums or mucilages or synthetic polymeric substances fer high viscosity upon the system asawhole. for imparting slip when desired, or binders such as The invention will now be described by way of eX- starch, starch lower alkyl ethers, starch lower alkoxyamples. ethers, starch lower alkyl carboxy ethers, starch lower EXAMPLES Parts by Weight of Materials (Expressed on tho As sold" basis) Example No Controls 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 015.18 sodium alkene sulphonate 100 J0 80 80 60 60 60 50 50 40 30 20 10 C-is magnesium alkene sulphonate C1445 Sodium alli ene suophonato.- 014.15 Dobanol sodium sulphate Cian synthetic alcohol sulphate.- Tallow alcohol soduim sulphate... Slip inducing agent Titanium dioxide- 2() alkyl sulphonate ethers, cellulose lower alkyl ethers, celluof vinyl alcohol, maleic acid, acrylic acid, itaconic acid, pyrrolidone, or allyl alcohol, polyoxyalkylene oxides particularly polyethylene oxides e.g. Carbowaxes (RTM), Polyoxes (RTM), a proportion of the polymerised monomer units optionally carrying a corboxy, sulphate, sul- Other typical compositions are:

Parts by Weight Example 19 20 21 phonate, phosphate or phosphonate ionising group; colour- Igepon MRTM) 60 70 50 ing agents, pigments, bactericides, fungicides, preserya- Cn nsodium alkene sulphonate 40 50 tives, perfumes, sequestering agents, glucose, glycerlne Ad' Waiter 10 10 10 35 hydrogen bond forming substances such as urea; electrolytes such as sodium chloride, sodium sulphate, sodium (Note that olens catalytically formed from ethylene lactate, and Sodium phosphate, pyrophosphate or poly.

and also those made by dehydration of fatty alcohols phosphate from natural sources, are mixtures of even-numbered What is Claimed is;

carbon atom chains, whereas those derived from cracked 40 1 A synthetic detergent toilet bar which consists esparafns are mixtures 0f both Odd and even-numbered sentially of (a) from about 30% to about 70% by weight Cai'bOH atom CilaiIlS- The Cuts quoted in Ithe above eX- of a mixture of an alkali metal or alkaline earth metal amples are l0 be taken t0 include bOll'l even-numbered salt of an alkene sulphonic acid having 11-24 carbon Chains Only and eVeIl-PUS-Odd numbered Chains, avefagatoms and a hydroxy-alkane sulphonate, said hydroxymg about the Same mean mOleCUlal" Weight and Spanning alkane sulphonate being a mixture of alkane-S-hydroxyapproximately the same range in numbers `of C atoms 1sulphonate, alkane-4-hydroxy-l-sulphonate and alkanein the chains.) Z-hydroxy-l-sulphonate, wherein no more than 2% by The tablets used for this work were readily manufacweight of said mixture of hydroxy-alkane sulphonate is tured on laboratory scale equipment designed to reproduce the alkane-Z-hydroxy-l-sulphonate and the weight ratio as nearly as possible the conditions of full scale manuof the salt to the hydroxy-alkane sulphonate mixture is facture. The formulations were milled three times on a about 2 to 1, together with (b) from about 70% to about three rollered mill followed by crimping and plodding 30% by weight of a primary alkyl sulphate wherein the through a die giving a bar of cross section 1% x 3%, alkyl group has from 14-20 carbon atoms. which was stamped to tablets measuring 1%" x X 2. A bar according to claim 1 wherein said sulphonate 25/5. The bars so produced were satisfactory in appear- 55 has 14- 20 carbon atoms, ance and in wear and storage properties and were sub- 3. A bar according to claim 1 wherein said sulphate stantially non-irritant. is a mixture of synthetic primary alcohol sulphates of 14 Whilst the invention has been specifically described in and 15 carbon chain lengths, and which have about 30% the examples, mainly with reference to sodium salts, other branching at the 2-position. alkali metal or alkaline earth metal salts of the suphonates 4, A bar according to claim 1 wherein said salt is a or alkali metal sulphates may be used Similarly- It S 3180 mixture of salts of different cations being selected from POSSible t0 employ mixed CaiOIlS, -e i0 use, as alkene the group of sodium, potassium, magnesium and calcium. sulphonate component, a mixture selected from sodium, potassium and magnesium alkene sulphonates. It is also References Cited possible to employ alkene sulphonates of differing carbon UNITED STATES PATENTS chain length in conjunction with each other. The required blend of alkene sulphonates may be obtained by sulpho- 3,186,948 6/ 1965 Sweeney 252-161 nation of a blend of olens of the desired distribution of 3,346,629 10/ 1967 BI'OUSSalian 260-513 carbon chain lengths, or by admixture of sulphonation l products of olens of single chain lengths. MAYER WEINBLATT, Primary Examiner Minor amounts of other ingredients which may be P E WILLIS Assistant Examiner added, known to those skilled in the art, include the following: lather modifiers such as higher aliphatic straight U.S. Cl. X.R.

or branched parafins, fatty acids, fatty alcohols, fatty 252-138 amides, fatty alkylolamides, fatty ureides, or fatty guan- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,523,089 Dated August 4, 1970 Inven COT (S )ward Garrett It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column l, line 18, the word "alkene" should read alkane.

Column 2, lines 8 through 16 delete "and provided with.

disulphonic acids" inclusive and insert in place thereof --and provided with a means for removing the heat of reaction. A reaction product is obtained which, on acidic hydrolysis followed by neutralisation, or by alkaline hydrolysis yields salts of sulphonic acids These sulphonic acids are complex mixtures of alkane hydroxy sulphonic acids and alkene acids with a proportion of sulphonic acids of low equivalent weight which are conveniently termed "di-sulphonic acids", without implying that they are wholly true disulphonic acids.

Column 4, line 25, the word "alpho" should read -alpha.

Columns 5 and 6 description under "Example No. line 3,

"C14 5" should read -C 4..l8, and the word "suophonate" shoul read sulphonate.

line l2 "28 Heater" should read 28H water.

Column 5, line 22, the figure "19" should read l8.

line 34 "Cl5 30" should read -Cl6 20.

Column 6, line 30, the word "corboxy" should read carboxy.

FORM F30-1050 (1D-69) SIGNED AND SEALED (SEAL) FEB am Mew EEB. 2,1971 Edwanlnddlqk. mm2. ma a Attesving Offi, rEvaluaciones of Patents UCMMDC 503754369 i LLI. IOVIIIIIINT FIINTING OFFICII Il" b-lll-III 

